Poly-(aromatic ether) compositions and method of making same



3 000 839 PGLY-(AROMATIC ETHEll) COMPOSITIONS AND METHOD OF MAKING SAME Earl H. Rosenbrock, Auburn, and James D. Doedens,

Midland, Mich., assignors to The Dow Chemicai Comp'any, Midland, Mich., a corporation of Delaware No Drawing. Filed Sept. 28, 1959, Ser. No. 842,603

4 Claims. (Cl. 260-) This invention concerns the preparation of polymeric 3,000,839 Patented Sept. 19, 1961 te aet as-a decemposition catalyst for the evolunone: undesirable running or flowing out. Since the cataaromatic ethers, condensation products or polyhaloi'ne'thylated aromatic ethers having more than one chloromethyl or bromomethyl group per aromatic ether molecule.

More particularly it concerns foamed condensation poly mers of polyhalomethylated diphenyl oxides, prepared by using a ferrous or ferric phosphate or mixture thereof both as a polymerization catalyst and as a foam modifier.

The preparation of foamed condensation polymers of polyhalomethyl diphenyl oxides, PHMDPOs, by which designation is included chloromethyl and bromon'iethyl dii phenyl oxides (CMDPO and BMPDO, respectively) conraining more than one halomethyl group per aromatic ether molecule, such as dihalomethylated diphenyl oxide,

trihalomethylated diphenyl oxide and tetrahalome'thylated diphenyl oxide and their methyl substituted homologs, hereinafter designated as DCMDPO, Tri-CMDPO, Tet- CMDPO, DBMDPO, Tri-BMDPO, Tet-BMDPO and commercial or technical grade mixtures thereof which may contain small amounts of mono-CMDPO or mono- BMDPO and unreacted diphenyl oxide and wherein the chloromethyl or bromomethyl substituents are in the ortho and/or para positions with respect to the ether oxygen, have usually been carried out by heating them in the presence of a Friedel-Cra'ft's catalyst, e.g., zinc chloride, ferric chloride, aluminum chloride, bereanueride, 'etc., as described in U.S. pateiit appucaaan Serial No. 530,891, filed August 26, 1955, now U.S. Patent 2,911,380.

In the preparation of such foamed condensation products wherein HMDPO having more than one chloromethyl or bromomethyl g oup per molecule is heated to a temperature suflicient to cause reaction with foaming due to evolution of hydrogen chloride or hydrogen bromide in the presence of a Friedel-Crafts catalyst, diificulty has been experienced in uniformly dispersing such catalysts because of their insolubility so as to get a relatively homogeneous reaction mixture whereby a uniformly foamed reaction product can be obtained. Consequently, with such prior art catalyzed reaction mixtures it liasbeen necessary to use extreme care to insure obtaining completely thermoset products which do not shrink thereaf er, This has meant using prolonged agitation at an elevated temperature, still without complete satisfaction. Also,- prior art compositions are too fluid, in many instances;

and flow out unduly instead of foaming straight up.

In accordance with this invention, it has been discov ered that a small amount of anhydrous ferrous or ferric phosphate or their mixture, e.g., from about As to about 2 weight percent, HMDPO basis, can be uniformly dislyst is readily dispersed and is at least partially soluble in the reaction mixture, depending upon the amount used, prfildnged agitation and heating to promote adequate disp'ision are 156th a'vdided.

The following examples are in illustration and not in limitation er the invention. Parts and percentages therein are by weight.

EXAMPLE 1 A 4" x 6' pyrex glass plate marked with a horizontal line across the top 'Was tilted at 30 to the horizontal in the laboratory oven and heated to the desired temperature. PHMDPOs "with various additives were then'tes'ted by putting two drops of the formulation on the top line and the distance of run-down before cure was measured, as follows.

The advantages gained with ferrous and ferric phosphate are ease of dispersion when mixed with HMDPOs and a lower cure temperature with less run. In all cases, are products thereby obtained are completely thermoset,

relatively uniformly foamed condensation polymers; Resuits renew.

- Table I REDUCTION IN FLOW ha nium-RENT TEMPERATURES 1 nunrernehesat Material Additive Perigi'eht n-.. i

Gone. O.-.

CMDPO 17.3"" rent-ti 1 5 4 a I 259 5.5 '4 3 D9 0.25 e 5.25 4 Do. 0.125 '7 '6. s 5. a 1' Do none...

1 Diphenyl ,oxidento-CMDPO--- oMD1 o io in ro ppiii-0 P0- Tet-OMDPO Thermoplastlclhrank.

persed therein and at least partially dissolved lay-simple EXAMPLE 2 The foam character of several HMDPOs Was studied with various additives at 100 and at 150 'C. "The formulations were placed in beakers and heated in a labor'a story oven at the given temperatures. After a timesufficient for a complete cure, the density and type team were characterized. "Results follow.

x o,ooo,eso v I I 3 I I I 4 Table II FOAM CHARACTER 100 6.

Material Catalyst Percent Temp., Time, Density, Properties Cone. 0. Min. 1b./cu. ft.

FOAM CHARACTER 150 0.

Percent Temp. Foam Material Catalyst Gone. O. Density Foam Type 1b.]cu. It.

CMDPO (17.5% 01). Ferrous 1 150 0.67 Large uniform I phos- Euros few blow phete. oles, thermoset, no shrink- I age. 150 0. 73 Do. 150 1.08 Do. 150 I z. 25 Small pore foam, few large blow 1 holes, thermo- I I I I I I I plastic, shrank. OMDPD (18.5%01)- Ferrous 1 150 I v 2.3 Small pore foam, phoa few large blow phate. holes, thermoset. no shrink I ago. Do none. I I e I 150 4. 5 Very poor roam,

large blow holes, thermoplastic shrank. CMDPO (23.5% Ferrous 150 8. 1 Heavy dense foam,

01). phos- I thermoset no phate. I shrinkage.

Do n 150 16.0 Large blow holes,

r10 foam, thermoplestlc.

Mole percent 1 o-GMDPO 0.

CMDPO 4. 7 -DOMDPO. 35.4 p,p-DCMDP 37.7 tri-CMDPO 21. 1 tetrwGMDPO 0.5-1.0

EXAMPLE 3 I EXAMPLE. 4

Ferrous phosphate as a catalyst and modifier of foams 3 1 Ferric phosphate was dispersed in CMDPO (23.5% prepared from poly-CMDPOs was dompared with zinc Cl) and foamed at 75 C. for ca. one minute with the chlorlde at 70 C., as follows: followmg results.

I FOAM CHARACTER 70 0.

Material Catalyst Percent Temp., Time, Density Properties Gone. 0. Min. lb./ou. ft.

OMDPO Ferrous I 1 70 6 I 2.4 Large pore (17.5950 p os- WM. l slzeioam I phate. with few blowholes, thermoset, no shrink- I age. Do 21101,... 1 70 80 Dldnotpoly- I V merize. CMDPO Ferrous l 70 I 3.8 Large pore (23.5%01). I phos' I II I I s1ze,heovy 'phater I I cellwalls A with few blowholes, thermoset, I V no shrinkl age. Do ZnCla..... 1 70- I v 30 Dldnptpolymerrze. OMDPO none.. 70 6O Do.

DPO none 70 60 Do. 123.5%01). I I I l 3,000,839 5 Percent FePO Properties 2. The method of claim 1, wherein the halomethyl sub- 0.5 Fine pore size foam few blowholes stituents are chloromethyl groups thermoset no shrinkage 3. A composition for making foamed condensation 10 D o products the essential ingredients of which consist of a 6 member of the group of poly(halomethyl) diphenyl ox- What is claimed is:

-1. A method for making a foamed condensation prodmet by heating at a temperature between about 50 and 150 C. for a time sufiicient to evolve hydrogen halide and to form a foamed, resinous, condensation product, a member of the group consisting of poly(halomethyl) diphenyl oxides having more than 1 and up to 4 halomethyl substituents of the group consisting of chloromethyl and bromomethyl per diphenyl oxide unit and mixtures thereof containing from about to about 2 weight percent of one of the group consisting of ferrous phosphate, ferric phosphate and mixtures thereof dispersed therein.

ides having more than 1 and up to 4 halomethyl substituents of the group consisting of chloromethyl and bromoethyl per diphenyl oxide unit and mixtures thereof and about /2 to about 2 weight percent of one of the group consisting of ferrous phosphate, ferric phosphate and mixtures thereof dispersed therein.

4. The composition of claim 3, wherein the halomethyl substituents are chloromethyl groups.

References Qited in the file of this patent UNITED STATES PATENTS 2,911,380 Doedens Nov. 3, 1959 

1. A METHOD FOR MAKING A FOAMED CONDENSATION PRODUCT. BY HEATING AT A TEMPERATURE BETWEEN ABOUT 50* AND 150*C. FOR A TIME SUFFICIENT TO EVOLVE HYDROGEN HALIDE AND TO FORM A FOAMED, RESINOUS, CONDENSATION PRODUCT, A MEMBER OF THE GROUP CONSISTING OF POLY(HALOMETHYL) DIPHENYL OXIDES HAVING MORE THAN 1 AND UP TO 4 HALOMETHYL SUBSTITUENTS OF THE GROUP CONSISTING OF CHLOROMETHYL AND BROMOMETHYL PER DIPHENYL OXIDE UNIT AND MIXTURES THEREOF CONTAINING FROM ABOUT 1/8 TO ABOUT 2 WEIGHT PERCENT OF ONE OF THE GROUP CONSISTING OF FERROUS PHOSPHATE, FERRIC PHOSPHATE AND MIXTURES THEREOF DISPERSED THEREIN. 